Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
  • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
  • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
  • C07D207/333—Radicals substituted by oxygen or sulfur atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
  • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
  • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
  • C07C255/38—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by esterified hydroxy groups
  • C07C255/39—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by esterified hydroxy groups with hydroxy groups esterified by derivatives of 2,2-dimethylcyclopropane carboxylic acids, e.g. of chrysanthemumic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
  • C07C69/743—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a three-membered ring and with unsaturation outside the ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
  • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
  • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
  • C07D209/49—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide and having in the molecule an acyl radical containing a saturated three-membered ring, e.g. chrysanthemumic acid esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
  • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
  • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
  • C07D277/24—Radicals substituted by oxygen atoms

Definitions

• novel compounds of the invention have the formula ##STR2## in all its possible stereoisomer forms and mixtures thereof wherein X is selected from the group consisting of hydrogen, halogen and alkyl, alkenyl, alkynyl and cycloalkyl of up to 8 carbon atoms optionally substituted by at least one halogen, Y is selected from the group consisting of a) alkyl, alkenyl, alkynyl and cycloalkyl of up to 8 carbon atoms optionally substituted with at least one member of the group consisting of halogen, --CN, --OH and alkoxy of 1 to 7 carbon atoms, b) aryl and aralkyl of up to 16 carbon atoms optionally substituted with at least one member of the group consisting of halogen, alkyl and alkoxy of 1 to 8 carbon atoms, --(CH 2 ) m --SiAlk 1 ) 3 , --(CH 2 ) n --OAlk 2 ,
• X or Y is halogen, it is preferably fluorine, chlorine or bromine and when X or Y is alkyl or cycloalkyl, it is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, vinyl, 1,1-dimethyl-allyl, ethynyl, propynyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, all optionally substituted by at least one fluorine, chlorine or bromine with X preferably being CF 3 .
• Aryl is preferably phenyl and aralkyl preferably is benzyl or phenethyl.
• Alk 1 , Alk 2 and Alk 3 preferably are methyl, ethyl or propyl.
• the alkyl or alkoxy is preferably methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl or tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy.
• the halogen is preferably fluorine, chlorine or bromine.
• X is hydrogen or fluorine or trifluoromethyl
• Y is hydrogen
• Y is alkyl of 1 to 6 carbon atoms, for example methyl, isopropyl or tert-butyl
• Y is Si(Alk 1 ) 3 in which Alk 1 has the previous meaning, for example methyl.
• R is selected from the group consisting of a) alkyl of 1 to 18 carbon atoms, b) benzyl optionally substituted by at least one member of the group consisting of halogen, alkyl, alkenyl, alkynyl, cycloalkyl, --O alkyl, --O alkenyl, --O alkynyl, --Salkyl, --Salkenyl and --Salkynyl, all containing up to 8 carbon atoms and optionally substituted by at least one halogen, --NO 2 , +CN and --NH 2 , ##STR3##
• R 1 is hydrogen or methyl
• R 2 is monocyclic aryl or --CH 2 --C ⁇ CH
• a is hydrogen or methyl
• R 3 is aliphatic of 2 to 6 carbon atoms with at 6 least one carbon-carbon unsaturation
• R' 1 and R' 2 are individually selected from the group consisting of hydrogen, halogen, alkyl of 1 to 6
• Especially preferred compounds of Formula I are those where R is ##STR6## wherein Z is hydrogen, fluorine, NH2, cycloalkyl, alkyl, alkenyl or alkynyl, O-alkyl, O-alkynyl, S-alkyl and S-alkenyl of up to 8 carbon atoms, optionally substituted by at least one halogen, preferably fluorine.
• Z is H, F, CH 3 , CF 3 , OCF 3 , OCHF 2 , CH 2 C.tbd.CH and CH 2 --CH ⁇ CH 2 .
• the most preferred compounds are those of Examples 1, 14, 22, 29, 30, 35, 39, 40, 54 and 55.
• the most preferred compounds are those of Examples 33, 35, 43 and 45.
• the process for the preparation of a compound of Formula I comprises reacting an acid or a functional derivative thereof of the formula ##STR8## in which X and Y have the above definitions with an alcohol of the Formula
• the esterification of the acid of Formula II with the alcohol of Formula III can be carried out in the presence of a tertiary base such as pyridine and can be advantageously carried out in the presence of a mixture of pyridine, dicyclohexylcarbodiimide and 4-dimethylamino-pyridine.
• the esterification can also be carried out by reacting a chloride of acid II on the alcohol of Formula III or on a metallic derivative of the alcohol such as a silver salt.
• the compounds of Formula II used as starting products for the process of the invention are new products and are in themselves a subject of the present invention.
• Detailed examples of the preparation of the compounds of Formula II are given hereafter in the experimental part, their preparation can be schematized as follows: ##STR9##
• R' is alkyl of 1 to 18 carbon atoms or a remainder of an acid used in the pyrethrinoid series and Hal is bromine or chlorine or iodine ##STR10## If desired, the stereoisomers obtained are separated.
• novel pesticidal compositions of the invention are comprised of a pesticidally effective amount of at least one compound of Formula I and an inert carrier. They are useful for combatting parasites of vegetation of the soil or the above ground plants, parasites of premises and parasites of warm-blooded animals.
• the products of the invention can be used for combatting parasitic insects, nematodes and acaridae of vegetation and animals.
• a particular subject of the invention is the use of the compounds of Formula I for combatting parasites of warm-blooded animals.
• the products of Formula I can also be used for combatting insects and other parasites of the soil, for example Coleoptera, such as DIABROTICA, click beetles and May beetle grubs, Myriapoda such as scutigeridae and blanjules, and Diptera such as cecydomia and Lepidoptera such as owlet moths.
• Coleoptera such as DIABROTICA
• Myriapoda such as scutigeridae and blanjules
• Diptera such as cecydomia and Lepidoptera such as owlet moths.
• the products of Formula I can also be used for combatting insects in premises, for combatting in particular flies, mosquitoes and cockroaches.
• the products of Formula I are more photostable and are not very toxic to mammals.
• the products of Formula I can also be used for combatting parasitic acaridae and nematodes of vegetation.
• the compounds of Formula I can also be used for combatting parasitic acaridae of animals, for combatting for example ticks and notably ticks of the Boophilus species, those of the Hyalomnia species, those of the Amblyomnia species and those of the Rhipicephalus species, or for combatting all sorts of mites and notably the sarcoptic mite, the psoroptic mite and the chorioptic mite.
• a subject of the invention is the composition intended for combatting parasites of warm-blooded animals, parasites of premises and of vegetation, characterized in that they contain at least one of the products of Formula (I) defined above, notably the products of Examples 1, 14, 22, 29, 30, 39, 40 and 41 or also those of Examples 54 and 55 and quite particularly those of Examples 33, 35, 43 and 45.
• a particular subject of the invention is the insecticide compositions containing as active ingredient at least one of the products defined above.
• compositions are prepared according to the usual processes of the agrochemical industry or the veterinary industry or the animal nutrition products industry.
• compositions intended for agricultural use and for use in premises can optionally have added to them one or more other pesticide agents.
• These compositions can be presented in the form of powders, granules, suspensions, emulsions, solutions, aerosol solutions, combustible strips, baits or other preparations usually employed for the use of this type of compound.
• these compositions contain, in general, a vehicle and/or a non-ionic surfactant, ensuring, moreover, a uniform dispersion of the constitutive substances of the mixture.
• vehicle used can be a liquid, such as water, alcohol, hydrocarbons or other organic solvents, a mineral, animal or vegetable oil, a powder such as talc, clays, silicates, kieselguhr or a combustible solid.
• the insecticide compositions according to the invention preferably contain 0.005% to 10% by weight of active ingredient.
• compositions according to the invention are used in the form of fumigant compositions.
• compositions according to the invention can therefore be advantageously constituted, for the non-active part, of a combustible insecticide coil, or also of an incombustible fibrous substrate.
• the fumigant obtained after incorporation of the active ingredient is placed on a heating apparatus such as an electric. emanator.
• the inert support can be, for example, composed of pyrethrum marc, Tabu powder (or Machilus Thumbergii leaf powder), pyrethrum stem powder, cedar leaf powder, sawdust (such as of pine sawdust), starch and coconut shell powder.
• the dose of active ingredient can then be, for example, 0.03 to 1% by weight.
• the dose of active ingredient can then be, for example, 0.03 to 95% by weight.
• compositions according to the invention for use in premises can also be obtained by preparing a sprayable oil based on the active ingredient, this oil soaking the wick of a lamp and then being set alight.
• the concentration of active ingredient incorporated in the oil is, preferably, 0.03 to 95% by weight.
• a subject of the invention is the acaricide compositions containing as active ingredient at least one of the products of formula I defined above.
• the insecticide compositions according to the invention can optionally have added to them one or more other pesticide agents.
• the acaricide and nematicide compositions can be presented in particular in the form of powder, granules, suspensions, emulsions, solutions.
• wettable powders are preferably used for foliar spraying, containing 1 to 80% by weight of active ingredient, or liquids for foliar spraying containing 1 to 500 g/l of active ingredient. Powders can also be used for foliar dustings containing 0.05 to 3% of active ingredient.
• liquids for soil treatment are preferably used containing 300 to 500 g/l of active ingredient.
• acaricide and nematicide compositions according to the invention are used, preferably, at doses comprised between 1 and 100 g of active ingredient per hectare.
• the compounds of formula (I) have an excellent general tolerance, and therefore a subject of the invention is also the products of formula (I), for combating in particular illnesses caused by ticks and mites in man and animals.
• the products of the invention are notably used for combating lice in a preventative or curative manner and for combating scabies.
• the products of the invention can be administered externally, by spraying, by shampooing, by bathing or painting-on.
• the products of the invention for veterinary use can also be administered by painting on the spine according to the so-called "pour-on” method.
• products of the invention can be used as growth regulators.
• a subject of the invention is the combinations endowed with insecticide, acaricide or nematicide activity, characterized in that they contain as active ingredient, on the one hand at least one of the compounds of general formula (I), and on the other hand, at least one of the pyrethrinoid esters chosen from the group constituted by the esters of allethrolone, of 3,4,5,6-tetrahydrophthalimidomethyl alcohol, of 5-benzyl-3-furyl methyl alcohol, of 3-phenoxybenzyl alcohol and of alpha-cyano-3-phenoxybenzyl alcoholswith chrysanthemic acids, by the esters of 5-benzyl-3-furyl methyl alcohol with 2,2-dimethyl-3-(2-oxo-3-tetrahydrothio-phenylidenemethyl)-cyclopropane-1-carboxylic acids, by the esters of 3-phenoxybenzyl alcohol and of alpha-cyano-3-phenoxybenzyl alcohol with 2,2-dimethyl-3-(2,2-
• a solution of 1.75 g of dicyclohexylcarbodiimide and 3 cm 3 of methylene chloride is added at 0°/+5° C. to a solution containing 2.12 g of [1R-[1alpha, 3alpha(Z)]] 2,2-dimethyl-3-[4-(trimethylsilyl) but-1-en-3-ynyl] cyclopropane carboxylic acid, prepared as indicated hereafter, 20 cm 3 of methylene chloride, 2 g of 2,3,5,6-tetrafluoro 4-(2-propynyl) benzyl alcohol and 20 mg of dimethylamino pyridine.
• the reaction mixture is maintained under agitation for one hour at 0°/+5° C.
• the reaction mixture is maintained under agitation while adding at 20° C., 0.91 g of bis(triphenylphosphine) palladium dichloride and 0.16 g of copper iodide.
• the reaction mixture is maintained under agitation for 5 hours at 45° C., then for 16 hours at 20° C. It is filtered and the filtrate is brought to dryness. 100 cm 3 of a saturated aqueous solution of sodium acid phosphate is added. Extraction is carried out with isopropyl ether. The organic phases are united, dried, filtered and brought to dryness.
• Aromatic 1642, 1604, 1499 cm -1
• Example 37 The product was obtained from Example 37 by following the operating method of Example 36.
• Rf approx. 0.25 (CH 2 Cl 2 --hexane 50-50).
• Rf approx. 0.2 (hexane--CH 2 Cl 2 7-3 ).
• Rf approx. 0.15 (hexane--CH 2 Cl 2 7-3 ).
• Example 1 The operation is carried out as in Example 1 starting with the [1R-[(1alpha, 3alpha(E)]] 3-(2-bromo-2-(trifluoro-methyl)] ethenyl cyclopropane carboxylic acid obtained according to EP 010874 or BF 2,392,964 and 1-(trimethylsilyl) propyn and the expected product is obtained.
• a homogeneous mixture is made of:
• a homogeneous mixture is made of:
• Granules were prepared containing 0.1% to 5% of active ingredients.
• test insects are last-stage larvae of Diabrotica.
• test insects are 4-day old female houseflies. The operation is carried out by spraying in a Kearns and March chamber using a mixture of acetone (5%) and Isopar L (petroleum solvent) as solvent (quantity of solvent used 2 ml per second). 50 insects per treatment are used. Checks are carried out every minute up to 10 minutes, then after 15 minutes and the KT 50 is determined by the usual methods.
• the products of the invention have a good activity.
• the tests are carried out by topical application of an acetone solution of the product to be tested, using an Arnold micro manipulator, on the dorsal thorax of the larvae. 15 larvae are used per dose of product to be tested. The larvae used are fourth stage larvae, that is to say about 10 days old when they are bred at 24° C. and 65% relative humidity. After treatment the individual larvae are placed on an artificial nutritional medium (Poitout medium).
• the mortality check is carried out 48 hours after treatment.
• Bean plants are used having 2 leaves infested with 25 females of Tetranychus Urticae per leaf and put under a ventilated hood under an illuminated ceiling with constant light.
• the plants are treated with a Fisher gun: 4 ml of toxic solution per plant of a mixture of equal volumes of water and acetone.
• the leaves are left to dry for 12 hours then the infestation is carried out.
• Mortality checks are carried out after 80 hours.
• the dose used is 5 g of product per hl.
• the lethal concentration 50 (LC 50) is determined.
• the products of the invention have a good activity.
• a contact-ingestion method is used.
• a bean leaf is treated with a Fisher gun and is then placed in a plastic Petri dish on a circle of damp paper. The treatment is carried out using 2 ml of an acetone solution of product to be tested (1 ml per leaf surface).
• the insect infestation is carried out after the leaf has been dried. The insects are kept in contact with the leaf for one hour. The insects are placed on non-treated leaves and the mortality is checked after 24 hours.
• the test is carried out on 12-week old male cockroaches (Blattella germanica). The operation is carried out by direct spraying in a 13.5 cm diameter glass chamber.
• the product is put in solution in Isopar. 0.75 ml of solution is sprayed for 2.5 seconds over 20 cockroaches which have been placed beforehand in the chamber.
• the percentage of cockroaches knocked down after 5 minutes at a dose of 100 mm/l is determined.
• the products of the invention in particular the products of Examples 22, 32, 34, 48, 49, 50, 51 and 52, have a good activity.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Agronomy & Crop Science (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1992
  • 1992-02-21 FR FR9202009A patent/FR2687665A1/fr active Granted
  • 1992-12-17 US US07/992,452 patent/US5336670A/en not_active Expired - Fee Related

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